Pentanary Oxythiogermanates Ba3MGe3O2S8 (M = Ca, Zn) Featuring [Ge3O2S8]8- Trimers and {[MGe3O2S8]6-}∞ Chains: Structural Chemistry and Physical Properties.

Oxychalcogenides are increasingly attracting wide attention because they contain multiple anions that may combine the advantages of oxides and chalcogenides. In this work, two new pentanary oxythiogermanates, Ba3MGe3O2S8 [M = Ca (1), Zn (2)], were synthesized by a high-temperature solid-state reaction. They crystallize in the orthorhombic space group Pnma, and their structures contain isolated [Ge3O2S8]8- units constructed by one [GeO2S2] and two [GeOS3] tetrahedra that link with M2+ ions to build the {[MGe3O2S8]6-}∞ chain, representing a new type of oxythiogermanate. Notably, a [ZnS5] square pyramid exists in 2. Their structural chemistry and relationship with relevant structures are analyzed. 1 and 2 exhibit wide band gaps of 3.93 and 2.63 eV, birefringences of 0.100 and 0.089 at 2100 nm, respectively, and also obvious photocurrent responses. This work may be extended to a family of AE3MIIMIV3O2Q8 (AE = alkali-earth metal; MII = Ca, Zn, Cd, Hg; MIV = Si, Ge, Sn; Q = S, Se), and further systematic survey on them can be performed to enrich the study of multifunctional oxychalcogenides.

Assembling carbon nitride quantum dots into hollow fusiformis and loading CoP for photocatalytic hydrogen evolution.

The self-assembled carbon nitride quantum dots (CNQDs) has been largely advanced owing to the structure-relative photocatalytic activities, especially its electronic structure, which can be regulated by defects, functional groups, and doping. However, there are still issues such as wide band gaps for the assembles and severe recombination of photoinduced charges. Herein, we demonstrate the self-assembly of CNQDs into fusiform hollow superstructures (CNFHs), induced by hydrogen bonding between the terminal functional groups (-OH, -COOH, and -NH2). During the top-down assembly process, the hydrogen bonding dominates and initiates lateral cross-linking between adjacent CNQDs, which further twist into fusiform hollow structures. Benefitted greatly from the ultrathin and hollow nature of the superstructure that provides more exposed active sites, coupled with the introduction of phosphorus doping atoms into the framework induced narrowed band gap, CNFHs exhibits an 18-fold higher activity than the bulk counterpart toward photocatalytic hydrogen evolution after loading the CoP co-catalyst. This work presents a new platform to design and manipulate carbon nitride superstructures.

Tailoring coordination environments of single-atom electrocatalysts for hydrogen evolution by topological heteroatom transfer.

The rational design of carbon-supported transition-metal single-atom catalysts requires the precise arrangement of heteroatoms within the single-atom catalysts. However, achieving this design is challenging due to the collapse of the structure during the pyrolysis. Here, we introduce a topological heteroatom-transfer strategy to prevent the collapse and accurately control the P coordination in carbon-supported single-atom catalysts. As an illustration, we have prepared self-assembled helical fibers with encapsulated cavities. Within these cavities, adjustable functional groups can chelate metal ions (Nx···Mn+···Oy), facilitating the preservation of the structure during the pyrolysis based phosphidation. This process allows for the transfer of heteroatoms from the assembly into single-atom catalysts, resulting in the precise coordination tailoring. Notably, the Co-P2N2-C catalyst exhibits electrocatalytic performance as a non-noble metal single-atom catalyst for alkaline hydrogen evolution, attaining a current density of 100 mA cm-2 with an overpotential of only 131 mV.

Deep Circumflex Iliac Artery Flap Reconstruction in Brown Class I Defect of the Mandible Using a Three-Component Surgical Template System.

BACKGROUND: Computer-assisted surgery is widely used in mandibular reconstruction, but the process is not well described for cases using the deep circumflex iliac artery flap (DCIA) as the donor site. This study aimed to present a DCIA-based three-component surgical template system (3-STS) in patients with a mandibular Brown class I defect. METHODS: This retrospective cohort study compared clinical outcomes of mandibular reconstruction with DCIA flap using 3-STS or conventional surgical templates. The primary outcome of the study was the accuracy of reconstruction, and the secondary outcomes included surgical time and bone flap ischemia time. Surgery-related parameters and functional outcomes were also recorded and compared. RESULTS: Forty-four patients (23 in the 3-STS group and 21 in the control group) between 2015 and 2021 were included. Compared with the control group, the 3-STS group had higher accuracy of reconstruction, indicated by lower deviation in absolute distance (1.45 ± 0.76 mm versus 2.02 ± 0.89 mm; P = 0.034), and less deviation in coronal and sagittal angles (0.86 ± 0.53 degree versus 1.27 ± 0.59 degrees, P = 0.039; and 2.52 ± 1.00 degrees versus 3.25 ± 1.25 versus, P = 0.047) between preoperative and postoperative computed tomographic imaging. Surgical time and bone flap ischemia time were significantly reduced in the 3-STS group compared with the control group (median time, 385 minutes versus 445 minutes and 32 minutes versus 53 minutes, respectively; P < 0.001). In addition, masseter attachment was preserved in the 3-STS group but not in the control group. No differences were found in adverse events or other clinical variables. CONCLUSION: The 3-STS can improve accuracy, simplify intraoperative procedures to increase surgical efficiency, and preserve functionality in mandibular reconstruction for Brown class I defects. CLINICAL QUESTION/LEVEL OF EVIDENCE: Therapeutic, III.

Self-Destructive Copper Carriers Induce Pyroptosis and Cuproptosis for Efficient Tumor Immunotherapy Against Dormant and Recurrent Tumors.

Activating the strong immune system is a key initiative to counteract dormant tumors and prevent recurrence. Herein, self-destructive and multienzymatically active copper-quinone-GOx nanoparticles (abbreviated as CQG NPs) have been designed to induce harmonious and balanced pyroptosis and cuproptosis using the "Tai Chi mindset" to awaken the immune response for suppressing dormant and recurrent tumors. This cleverly designed material can disrupt the antioxidant defense mechanism of tumor cells by inhibiting the nuclear factor-erythroid 2-related factor 2 (NRF2)-quinone oxidoreductase 1 (NQO1) signaling pathway. Furthermore, combined with its excellent multienzyme activity, it activates NOD-like receptor protein 3 (NLRP3)-mediated pyroptosis. Meanwhile, cuproptosis can be triggered by copper ions released from the self-destructive disintegration of CQG NPs and the sensitivity of cancer cells to cuproptosis is enhanced through the depletion of endogenous copper chelators via the Michael addition reaction between glutathione (GSH) and quinone ligand, oxygen production from catalase-like reaction, and starvation-induced glucose deficiency. More importantly, CQG NPs-induced pyroptosis and cuproptosis can promote immunosuppressive tumor microenvironment (TME) remodeling, enhance the infiltration of immune cells into the tumor, and activate robust systemic immunity. Collectively, this study provides a new strategy to resist tumor dormancy, prevent tumor recurrence, and improve the clinical prognosis of tumors.

The performance tests of three-dimensional printing titanium alloy craniomaxillofacial bone plate: A preliminary preclinical study.

Background/purpose: Because of the complex anatomical structure of the maxillofacial skeleton, bending plates is necessary during surgery. The fast developing three-dimensional printing (3DP) technology has provided a new method for making personalized craniomaxillofacial bone plates. However, the properties of these bone plates remain unknown. This study evaluates the mechanical, fatigue, and morphological properties of these bone plates, which may provide data supporting future clinical applications. Materials and methods: The 3DP bone plate was fabricated by selective laser melting (SLM) and electron beam melting (EBM) technologies. Mechanical, surface, and defect analyses were performed to compare their properties with a standard machined sample. One-way analysis of variance was applied, with p < 0.05 considered significant. Results: The 3DP craniomaxillofacial bone plate had better bending strength than that of the standard machined plate (p < 0.01). Whereas the fatigue resistance of the 3DP bone plate needs to be improved in the future. Surface analysis indicated greater roughness of the 3DP bone plate (p < 0.01). However, the surface roughness could be significantly reduced by polishing the surface, which would meet the needs of clinical application after polishing. Further defect analysis revealed the internal defect inside the plate, which should be avoided to improve the mechanical strength of the printed sample in the future. Conclusion: The 3DP titanium craniomaxillofacial bone plate has good mechanical performance and surface morphology, meeting the requirements of clinical application. However, poorer fatigue resistance and a high number of internal defects should be modified in the future.

Intraoral Condylectomy with 3D-Printed Cutting Guide versus with Surgical Navigation: An Accuracy and Effectiveness Comparison.

This study compares the accuracy and effectiveness of our novel 3D-printed titanium cutting guides with intraoperative surgical navigation for performing intraoral condylectomy in patients with mandibular condylar osteochondroma (OC). A total of 21 patients with mandibular condylar OC underwent intraoral condylectomy with either 3D-printed cutting guides (cutting guide group) or with surgical navigation (navigation group). The condylectomy accuracy in the cutting guide group and navigation group was determined by analyzing the three-dimensional (3D) discrepancies between the postoperative computed tomography (CT) images and the preoperative virtual surgical plan (VSP). Moreover, the improvement of the mandibular symmetry in both groups was determined by evaluating the chin deviation, chin rotation and mandibular asymmetry index (AI). The superimposition of the condylar osteotomy area showed that the postoperative results were very close to the VSP in both groups. The mean 3D deviation and maximum 3D deviation between the planned condylectomy and the actual result were 1.20 ± 0.60 mm and 2.36 ± 0.51 mm in the cutting guide group, and 1.33 ± 0.76 mm and 4.27 ± 1.99 mm in the navigation group. Moreover, the facial symmetry was greatly improved in both groups, indicated by significantly decreased chin deviation, chin rotation and AI. In conclusion, our results show that both 3D-printed cutting-guide-assisted and surgical-navigation-assisted methods of intraoral condylectomy have high accuracy and efficiency, while using a cutting guide can generate a relatively higher surgical accuracy. Moreover, our cutting guides exhibit user-friendly features and simplicity, which represents a promising prospect in everyday clinical practice.

Oxygen Vacancy-Dependent Photocatalytic Selective Synthesis of an Unsaturated Amide on Spinel CuFe2O4.

Oxygen vacancies can change the physical and chemical properties of oxide semiconductors, which is applied to the field of ph otocatalysis, including water splitting, carbon dioxide reduction, and organic synthesis. However, the mechanism of oxygen vacancies in photocatalytic organic synthesis is still unclear. Herein, oxygen vacancies constructed on spinel CuFe2O4 nanoparticles were found to trigger the photocatalytic synthesis of an unsaturated amide with high conversion and selectivity. Such superior performance was attributed to the fact that the enriched surface oxygen vacancies could increase the charge separation efficiency and optimize the reaction path, which has been demonstrated both experimentally and theoretically.

Theoretical Insights on the Sensing Performance for Newly-synthesized Two-photon Fluorescent N2H4 Probes Based on Spirobifluorence.

The development of fluorescent probe for hydrazine (N2H4) detection has attracted much attention due to the important role of N2H4 plays in the fields of medicine, agriculture, biology and environments. In this paper, the optical properties and water solubility of two novel two-photon fluorescent molecular probes (Probe1 and Probe2) before and after the reaction with N2H4 are studied by using the density function theory. The results show that electronic distribution and transition dipole moment of the probes are obviously changed after the reaction with N2H4, thus the optical properties of the molecules are influenced and the detection of N2H4 are realized. In addition, photoinduced electron transfer processes for Probe1 and Probe2 in the presence of N2H4 are theoretically characterized, which explains the experimental observations from the microscopic mechanism. Special attention has been paid on the analysis of the two-photon absorption for the probes with the absence and presence of N2H4 by the response theory method. Both probes with good water solubility show large variation on the two-photon absorption cross section when reacts with N2H4. In particular, the two-photon absorption response of Probe2 is more obvious, so it possesses preferable two-photon fluorescence microscopic imaging ability. More importantly, the receptor effect on the sensing performances of the probes are demonstrated, providing a theoretical reference for the design and synthesis on more efficient two-photon fluorescence N2H4 probes. Our study provides necessary information on the response mechanism of the studied chemosensors and helps to establish the relationship between the structure and optical properties of two-photon fluorescence N2H4 probes.

The Midfacial Soft Tissue Changes After Anterior Maxillary Segmental Distraction Osteogenesis in Patients With Cleft: A 3-Dimensional Volumetric-Based Subunit Analysis.

BACKGROUND: Maxillary hypoplasia is common in patients with cleft lip and palate. In this study, the authors investigated the soft tissue changes in midfacial regions after anterior maxillary segmental distraction osteogenesis (AMSDO) in patients with cleft. METHODS: Eight patients with cleft lip and palate who underwent AMSDO were enrolled in this study. Spiral computed tomographic images were taken before surgery and 6-12 months after surgery to evaluate soft tissue changes after AMSDO. The midfacial area was divided into 6 regions of interest according to anatomical subunits. The average movements of each region were calculated using volumetric changes and preoperative region surface areas. RESULTS: The upper lip on both sides has the most anterior movement (5.22±0.86 and 5.14±0.84 mm), supracommissural regions have a little less movement (4.11±0.55 and 3.81±0.67 mm), paranasal regions have the least movement (3.37±0.47 and 3.15±0.36 mm). The corresponding regions of interest showed no significant difference on the cleft side versus the noncleft side. CONCLUSIONS: Anterior maxillary segmental distraction osteogenesis can improve the soft tissue profile in patients with cleft, and there was no significant difference in soft tissue changes between the cleft side and the noncleft side.

Precise Intraoral Condylectomy With the Guide of Three-Dimensional Printed Template in a Mandibular Condylar Hyperplasia Patient.

PURPOSE: This study aimed to introduce an innovative method for mandibular condylectomy. A customized three-dimensional (3D) printed template is used to perform precise condylectomy in an intraoral approach. METHODS: Condylectomy combined with orthognathic surgery was used for the treatment of facial asymmetry secondary to unilateral condylar hyperplasia. The customized 3D printed osteotomy guide was placed with an intraoral approach under endoscopy, in order to perform a precise condylectomy. RESULT: With the customized 3D printed template, the condylectomy was performed more precisely, and the conventional extraoral incision was avoided. The osteotomy line was accurately transferred from the virtual surgical plan to the real surgery, which assured the precise resection. CONCLUSIONS: The intraoral approach combined with a 3D printed template provides a novel solution to perform the condylectomy precisely.

Computer-Aided Autogenous Coronoid Process Graft Combined With Median and Unilateral Sagittal Split Osteotomy for Late Reconstruction of Condylar Fracture and Occlusion after Trauma.

PURPOSE: This study proposes a high-precision surgical technique that combines both computer-aided design/computer-aided manufacturing (CAD/CAM) and the screw-track transfer technique for condylar and occlusal reconstruction. MATERIALS AND METHODS: A 43-year-old male patient with facial asymmetry, limited mouth opening, and malocclusion underwent condylar and occlusal reconstruction surgery. An autogenous cor-onoid process graft was performed by combining CAD/CAM and the screw-track transfer technique. RESULTS: The surgical plan was transformed successfully from preoperative virtual surgical planning to actual surgery; this was confirmed by merging the postoperative computed tomography images with the preoperative three-dimensional surgical design. The patient recovered well and had better occlusion and facial symmetry, as well as an increased degree of mouth opening post-surgery. No complications were observed. CONCLUSIONS: CAD/CAM combined with the screw-track transfer technique is a precise and feasible method that can be applied to autogenous coronoid process grafts. This approach can be used to reconstruct the condylar process and achieve a good occlusal relationship.

Alternating Current Electrolysis Enabled Formal C-O/O-H Cross-Metathesis of 4-Alkoxy Anilines with Alcohols.

While multiple bond metathesis reactions, for example olefin metathesis, have seen considerable recent progress, direct metathesis of traditionally inert C-O single bonds is extremely rare and particularly challenging. Undoubtedly, metathesis reaction of C-O bonds is one of the most ideal routes for the value-added upgrading of molecules involving C-O bonds. Reported here is a new protocol to achieve the formal C-O/O-H cross-metathesis via alternating current electrolysis. Featuring mild reaction conditions, the protocol allows readily available 4-alkoxy anilines and alcohols to be converted into a wide range of valuable products in highly regioselective and chemoselective manner. Moreover, the present strategy can be used in the late-stage modification of pharmaceuticals as well as biologically active compounds, which demonstrated the potential application.

Randomized Clinical Trial of the Accuracy of Patient-Specific Implants versus CAD/CAM Splints in Orthognathic Surgery.

BACKGROUND: The maxilla position is essential for the aesthetic and functional outcomes of orthognathic surgery. Previous studies demonstrated the advantages of patient-specific implants in orthognathic surgery. However, more data are needed to confirm the superiority of patient-specific implants over surgical splints created with computer-aided design/computer-aided manufacturing (CAD/CAM). This randomized controlled trial aimed to compare the accuracy of patient-specific implants and CAD/CAM splints for maxilla repositioning in orthognathic surgery. METHODS: Patients (n = 64) who required orthognathic surgery were randomly assigned to use either patient-specific implants (patient-specific implant group) or CAD/CAM surgical splints (splint group) to reposition the maxilla. The outcome evaluation was completed by comparing virtual plans with actual results. The primary outcome was the discrepancies of the centroid position of the maxilla. Other translation and orientation discrepancies of the maxilla were also assessed. RESULTS: The authors analyzed 27 patients in the patient-specific implant group and 31 in the splint group. The maxilla position discrepancy was 1.41 ± 0.58 mm in the patient-specific implant group and 2.20 ± 0.94 mm in the splint group; the between-group difference was significant (p < 0.001). For the patient-specific implant group, the largest translation discrepancy was 1.02 ± 0.66 mm in the anteroposterior direction, and the largest orientation discrepancy was 1.85 ± 1.42 degrees in pitch. For the splint group, the largest translation discrepancy was 1.23 ± 0.93 mm in the mediolateral direction, and the largest orientation discrepancy was 1.72 ± 1.56 degrees in pitch. CONCLUSION: The result showed that using patient-specific implants in orthognathic surgery resulted in a more accurate maxilla position than CAD/CAM surgical splints. CLINICAL QUESTION/LEVEL OF EVIDENCE: Therapeutic, I.

In situ TEM Characterization of Microstructure Evolution and Mechanical Behavior of the 3D-Printed Inconel 718 Exposed to High Temperature.

This in situ transmission electron microscopy work presents a nanoscale characterization of the microstructural evolution in 3D-printed Inconel 718 (IN718) while exposed to elevated temperature and an associated change in the mechanical property under tensile loading. Here, we utilized a specially designed specimen shape that enables tensile testing of nano-sized thin films without off-plane deformations. Additionally, it allows a seamless transition from the in situ heating to tensile experiment using the same specimen, which enables a direct correlation of the microstructure and the mechanical property of the sample. The method was successfully used to observe the residual stress relaxation and the formation of incoherent γ' precipitates when temperature was increased to 700°C. The subsequent in situ tensile test revealed that the exposure of the as-printed IN718 to a high temperature without full heat treatment (solutionizing and double aging) leads to loss of ductility.

A new method for individual condylar osteotomy and repositioning guides used in patients with severe deformity secondary to condylar osteochondroma.

BACKGROUND: Mandibular condylar osteochondroma (OC) could lead to facial morphologic and functional disturbances, such as facial asymmetry, malocclusion, and temporomandibular joint dysfunction. However, after condylar OC resection, the inaccurate reposition of the neocondyle still needs to be solved. The purpose of this study was to explore the feasibility of the condylar osteotomy and repositioning guide to reposition the neocondyle in the treatment of patients with severe deformity secondary to condylar OC. RESULTS: Three patients with severe deformity secondary to OC of the mandibular condyle were enrolled in this study. With the aid of condylar osteotomy and repositioning guide, condylar OC resection and repositioning were carried out, and the accuracy and stability of these guides were evaluated. All patients healed uneventfully, and no facial nerve injury and condylar ankylosis occurred. Compared with the computerized tomography scans in centric relation before surgery and 3 days after surgery, the results showed that the facial symmetry was greatly improved in all the patients. Also, after the superimposition of the condylar segments before surgery and 3 days after surgery, the postoperative reconstructed condyles had a high degree of similarity to the reconstruction of the virtual surgical planning. Observed from the sagittal and coronal directions, the measurements of condylar positions were very close to those of virtual surgical planning. Moreover, it also showed stable results after a 1-year follow-up. CONCLUSIONS: For patients with severe deformity secondary to condylar OC, condylar osteotomy, and repositioning guide was expected to provide a new option for the improvement of facial symmetry and occlusal relationship.

Application of Virtual Planning for Three-Dimensional Guided Maxillofacial Reconstruction of Pruzansky-Kaban III Hemifacial Microsomia Using Custom Made Fixation Plate.

PURPOSE: Pruzansky-Kaban III hemifacial microsomia (HFM) is a rare congenital facial deformity, and it is challenging to reconstruct the facial appearance. The aim of the present study was to describe a technique of application of virtual planning for three-dimensional (3D) guided maxillofacial reconstruction of Pruzansky-Kaban III HFM using custom made fixation plate. METHODS: With the help of 3D models, a preoperative virtual planning and surgical simulation were performed. Computer-aided design/computer-aided manufacture (CAD/CAM) patient customized guides and custom fixation plates were designed to reconstruct the maxillofacial skull intraoperatively. Assessment was achieved through evaluation of the postoperative effects, such as imaging, facial appearance recovery and operation time. RESULTS: Five patients with Pruzansky-Kaban III HFM were enrolled into this study. The results showed an exceptional accuracy between the preoperative virtual planning and the outcomes actually achieved postoperatively. Intraoperative measurements were no longer needed and the different surgical steps became more simple and easier. The total time was distributed as: 160 minutes for the surgical time, 40 minutes for preoperative virtual plan, and 80 minutes for designing the patient specific cutting guides and custom fixation plates. The operating time and tissue damage were reduced. All cases underwent uneventful healing without any complications. CONCLUSION: The technique of patient specific guides and custom fixation plates is a reliable method of conveying the virtual plan to the operative field with higher efficiency in patients with Pruzansky-Kaban III HFM.

Efficacy and economic benefits of a modified Valsalva maneuver in patients with paroxysmal supraventricular tachycardia.

BACKGROUND: A modified Valsalva maneuver (VM) has been suggested to be superior to the standard VM for conversion of paroxysmal supraventricular tachycardia (PSVT). AIM: To evaluate the efficacy and economic benefits of a modified VM in Chinese patients. METHODS: Patients with PSVT admitted to our center between October 2017 and September 2019 were randomly assigned to the modified and standard VM groups. Conversion via VM was performed up to three times. The primary outcome of the study was the success rate of PSVT conversion to sinus rhythm. The secondary outcomes included the incidence of adverse events, economic cost during the visit, and the degree of patient acceptance of the treatment. RESULTS: Overall, 361 patients were enrolled, with 180 allocated to the modified VM group and 181 to the standard VM group. Baseline characteristics were well matched in the groups. Overall, the modified VM group had higher success rates of PSVT conversion after single (47.78% vs 15.38%, P < 0.001) and multiple (62.22% vs 19.78%, P < 0.001) VM sessions. No significant differences in the incidences of adverse events and rates of patient acceptance were detected between the two groups (both P > 0.05). Moreover, the economic cost of the clinic visit was significantly lower for the modified VM group than for the standard VM group (P < 0.05). CONCLUSION: The modified VM may confer both therapeutic and economic benefits as compared with the standard VM for conversion of PSVT.

Wet chemical epitaxial growth of a cactus-like CuFeO2/ZnO heterojunction for improved photocatalysis.

Herein, a wet chemical epitaxial growth method was employed to fabricate a cactus-like CuFeO2/ZnO heterojunction for the photocatalytic reduction of benzaldehyde to benzyl alcohol. The 1D ZnO nanorods in the heterojunction make contact with the 2D CuFeO2 nanoflakes at the atomic level, therefore providing a fast charge transfer channel along the direction parallel to the CuFeO2c-axis, leading to efficient charge separation and improved photocatalytic performance.

Correction: Wet chemical epitaxial growth of a cactus-like CuFeO2/ZnO heterojunction for improved photocatalysis.

Correction for 'Wet chemical epitaxial growth of a cactus-like CuFeO2/ZnO heterojunction for improved photocatalysis' by Tengfei Jiang, et al., Dalton Trans., 2020, DOI: 10.1039/d0dt01813a.